Process for cleaning hydrocarbons from soils

ABSTRACT

A combination of parallel processes is disclosed to provide optimal re-mediation operations for contaminated soil. Soils with high levels of heavy petroleum hydrocarbons are directed to a thermal process for destruction in a combustion process. Carbon dioxide generated and recovered in the thermal process is employed as a solvent in a solvent process to clean other soils of petroleum hydrocarbons and certain chlorinated hydrocarbon compounds. In the solvent process, contaminated soils are run through a closed soil separator where the soils are washed with carbon dioxide. The carbon dioxide is then dried from the soil and the soil is sent for segregation. Soils with the lightest forms of hydrocarbon contamination (gasoline, etc.) are subjected to a vaporization process utilizing heat energy generated in the thermal process to heat the soil, under a partial vacuum, and the vapors generated are captured, condensed, and recovered as product.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a divisional application of application Ser. No.09/507,060, filed Feb. 21, 2000 now U.S. Pat. No. 6,688,318 (Notice ofAllowance mailed Sep. 23, 2003), which is a continuation-in-part ofapplication Ser. No. 08/864,597, filed May 28, 1997, which issued asU.S. Pat. No. 6,137,026; and which is a continuation-in-part ofapplication Ser. No. 09/181,110, filed Oct. 28, 1998, which issued asU.S. Pat. No. 6,024,029, and which was a divisional of application Ser.No. 08/730,974, filed Oct. 16, 1996, and which issued as U.S. Pat. No.5,906,806. Each of these applications is hereby incorporated byreference herein, in their entirety, for all purposes.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a process for decontaminating soil andwaste materials. More particularly, the present invention relates to acombination of processes including a thermal combustion process, asolvent wash process that utilizes carbon dioxide generated in thethermal process, and a vaporization process that utilizes heat energygenerated in the thermal process, which in combination are used toremove volatile organic compounds from soil and other waste which havevarious levels of contamination.

2. Description of the Related Art

For many years a major problem occurring with the development ofindustry, in general, and the energy and petrochemical industry, inparticular, has been the need to remove the oils and other hydrocarbonsthat have been spilled from contaminated soil. The processes of choicehave always been traditional thermal combustion processes, but the costof these processes and the collateral damage that they can cause to theenvironment makes this solution unattractive in many cases. Most soilcontamination is reported to be less than one percent (1%) by volume.The thermal processing of this material which contains very littlehydrocarbon contamination is expensive at the very least, and mostfrequently causes damage to the soil. Further, the effects of theairborne contaminates and the use of ambient air in the thermal processcan result in damage to a wide area.

Other treatment processes for contaminated soils lack the ability toclean or remediate the contamination. Burying soils in vaults has notbeen a viable or cost effective solution and the excavation andtransportation of contaminated soil leaves the high possibility ofscattering the pollution. The use of microorganisms or “microbes” haslittle value since much of the contamination either kills the organismsor they have little effect on the pollutant. Additionally, few peopledesire or will accept a sludge pit in their neighborhood.

It has been known to use carbon dioxide as a liquid near its criticalstate or as a fluid in its super-critical state to serve as anextractant for hydrocarbons from various materials. See, for example,U.S. Pat. No. 4,434,028. However, concern is now being raised over theenvironmental pollution resulting from emission of carbon dioxide.Carbon dioxide has been identified as one of many “greenhouse” gases andits increased level in the earth's atmosphere is thought likely tocontribute to an undesirable global warming effect.

It would be desirable to have a process that addresses and resolves mostif not all of these concerns and interacts proactively to provide anacceptable, non-polluting, cost effective solution to this major socialand environmental problem.

BRIEF SUMMARY OF THE INVENTION

The present invention is a combination of parallel processes thatprovide optimal remediation operations for contaminated soil. Soils withhigh levels of heavy petroleum hydrocarbons are directed to a thermalprocess for destruction in a combustion process. Carbon dioxidegenerated and recovered in the thermal process is employed as a solventin a solvent process to clean soils having moderate contamination withpetroleum hydrocarbons and chlorinated hydrocarbon compounds. In thissolvent process, contaminated soils are run through a closed soilseparator where the soils are washed with carbon dioxide. The carbondioxide is then dried from the soil and the soil is sent forsegregation. Additionally, soils with the lightest forms of hydrocarboncontamination, such as gasoline, etc., are subjected to a vaporizationprocess utilizing heat energy generated from the thermal process to heatthe soil under a partial vacuum. The vapors generated are captured,condensed, and recovered as product.

BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS

A better understanding of the present invention can be obtained when thedetailed description set forth below is reviewed in conjunction with theaccompanying drawings, in which:

FIG. 1 is a block flow diagram of an embodiment of the combined thermal,solvent, and vaporization processes;

FIGS. 2A, B, and C are a detailed flow diagram of an embodiment of thecombined thermal, solvent, and vaporization processes;

FIG. 3 is a block flow diagram of an embodiment of the thermal process;

FIG. 4 is a graphical representation of the effect of temperature on thespecific heat capacity of oxygen, carbon dioxide, and water;

FIG. 5 is a graphical representation depicting the impact of waterinjection and recirculation upon an embodiment of the thermal process;

FIG. 6 is a graphical representation of the impact of water injectionand recirculation gas on the percentage of carbon dioxide producedduring combustion;

FIGS. 7A and 7B depict a process flow diagram of an embodiment of thethermal process;

FIGS. 8A and 8B depict a process flow diagram of the embodiment of thethermal process shown in FIGS. 7A and 7B with additional optionalfeatures;

FIG. 9 is a process flow diagram of an embodiment of the solventprocess; and

FIG. 10 is a process flow diagram of an alternative embodiment of thesolvent process.

DETAILED DESCRIPTION OF THE INVENTION

As shown in FIG. 1, the process of the present invention combines athermal process 10 that includes a combustion step 12 with carbondioxide recovery 14, with a solvent process 20 for removing hydrocarbonsfrom contaminated soils utilizing carbon dioxide from the thermalprocess 10 as a solvent. The thermal process 10 includes a combustionstep 12 that utilizes oxygen rather than air for oxidation and whichutilizes a recycle to increase the combustion efficiency. The carbondioxide generated in the combustion step is recovered in a carbondioxide processing step 14. The recovered carbon dioxide is thenforwarded in a carbon dioxide distribution step 16 to the solventprocess 20. Thermal process 10 is referred to in the figures generallyas the ZEROS process. Solvent process 20 is referred to in the figuresgenerally as Biodynamics.

The solvent process 20 begins with a step 22 of introducing contaminatedsoil or other waste material and carbon dioxide from the distributionstep 16 into a soil processor. Soil processing step 24 uses carbondioxide as a solvent to extract hydrocarbons and other contaminants suchas chlorinated compounds. The carbon dioxide containing the extractedhydrocarbon and other contaminants is separated from the soil. Thecontaminated carbon dioxide can then be returned to the thermal process10 for combustion of the hydrocarbons and recovery of the carbondioxide.

After separation of the carbon dioxide, the soil is then subjected to asegregation step 28 in which soils containing metal contaminants areseparated for further treatment. The remaining decontaminated soils areremoved from the solvent process 20 in a removal step 30 for return tothe original site of removal or to other locations for use as refill.Soil contaminated with metals can be treated in an acid wash andneutralization process 32 to remove the metals. The treated soil is thenremoved from the system in a removal step 34 for return to the originalsite or to other locations for use as refill.

An alternative process 40 that can also be used in conjunction with thethermal process involves cleaning contaminated soil in place. Carbondioxide from the distribution step 16 is injected into the groundthrough a monitoring well in an injection step 42. The carbon dioxideacts as a solvent, picking up hydrocarbons, as it migrates through theearth and accumulating hydrocarbons in subsurface water. The hydrocarboncontaminated subsurface water and the carbon dioxide can then be pumpedto the surface in a recovery step 44. The contaminated water and carbondioxide can be treated in thermal process 10 to combust the hydrocarbonsand recover the decontaminated water and carbon dioxide.

FIG. 2 depicts a more detailed flow sheet of the thermal process 10, thesolvent process 20, and the vaporization process 50 of the presentinvention and the interaction between the processes when combined. Thiscombination allows for the treatment of all types or levels ofcontamination and the general remediation of a contaminated area withoutany air or water pollution. The present invention allows for thecomplete destruction of contamination while producing an environmentallybenign byproduct that aids and accelerates the remediation process.

Thermal Process

Thermal process 10 of the present invention utilizes pure oxygen forcombustion, but additionally utilizes a combination of water injectionand combustion gas re-circulation to moderate and control the combustiongas temperature achieved in the combustion chamber. The utilization ofoxygen for combustion, and water injection and re-circulated combustiongas for moderating combustion gas temperature, avoids the introductionof nitrogen into the combustion process. Nitrogen in a combustionprocess leads to the formation of pollution in the form of oxides ofnitrogen (NOx). Since air is composed of roughly 80% nitrogen by volume,the present invention by design avoids the employment of air as thesource of oxygen for combustion or as a means of moderating thecombustion gas temperature in the combustion chambers. Other reasons foravoiding the use of air in the present invention are the fact that ahigh volume of combustion gas would be produced per unit of fuelcombusted and the resulting combustion gas would contain a lowerpercentage of carbon dioxide making carbon dioxide recovery lessefficient.

Thermal process 10 begins by introducing soil 62, heavily contaminatedby hydrocarbons, a fuel stream 64 or other hydrocarbon containingstream, an oxygen stream 66, and a water stream 68 into a combustionprocess. The thermal process 10 uses oxygen for combustion, combinedwith re-circulation of combustion gas and water injection to moderatecombustion gas temperature, to avoid the necessity for introduction ofnitrogen into the system. This allows for a more efficient combustionprocess generating greater combustion to carbon dioxide and decreasingthe amount of emissions generated by the thermal process 10. Adecontaminated soil stream 70 is removed from the thermal process 10 forreplacement or refill. The thermal process of the present invention isdisclosed in U.S. Pat. No. 5,906,806 and Applicant's co-pendingapplication Ser. Nos. 08/730,974 and 09/234,036, each of which arehereby incorporated by reference in their entirety for all purposes.

As shown in FIG. 3, a fuel stream is injected into primary combustionchamber 210 along with a substantially pure oxygen stream and a waterstream. The fuel stream can be a combination of a clean hydrocarbonstream such as natural gas, methane, etc. and a waste stream such asliquid or soil wastes containing hydrocarbon. The fuel, oxygen, andwater streams are combusted in primary combustion chamber 210 and thecombustion product is then transferred to secondary combustion chamber212. In secondary combustion chamber 212, the combustion product isfurther combusted along with additional fuel, oxygen, and water streamsto produce a final reaction product stream. The reaction product streamis then introduced to an energy recovery boiler 214 or other means ofremoving and recovering heat energy from the reaction product stream.The cooled reaction product stream is then split with a portion of thecooled reaction product stream being recirculated to primary combustionchamber 210, a portion being recirculated to secondary combustionchamber 212, and a portion proceeding forward to combustion gas cleaningsystem 216. In combustion gas cleaning system 216, the cooled reactionproduct stream is treated to remove acidic components, residual organiccomponents, and finally to separate the water contained in the reactionproduct stream from the carbon dioxide. Carbon dioxide is thenintroduced into combustion gas recovery system 218 where it is purifiedand liquefied to produce a liquid carbon dioxide product. As will berecognized by those skilled in the art, implementation of thesecomponents of the present invention will reduce or eliminate the gasdischarge to the atmosphere.

Ideal complete combustion of a pure hydrogen fuel with pure oxygenyields carbon dioxide and water as the products of combustion. To insurehigh combustion efficiency, an excess of oxygen is required along withhigh temperature, high combustion gas turbulence, and long combustiongas residence time in the chamber(s) supporting the combustion process.These factors all contribute to contact opportunity between oxygenmolecules and molecules of hydrogen fuel(s) by producing robust mixingof the gases for long periods of time. The high temperature additionallyprovides the drive or ignition energy to produce the chemical reactionbetween the oxygen and fuel(s) when contact between molecules occurs.

Wagner teaches in U.S. Pat. No. 3,779,212 that a pure hydrogen fueloxidized with pure oxygen produces carbon dioxide, water, and carbonicacid as products of combustion. Wagner further teaches that the carbonicacid rapidly disassociates into carbon dioxide and water resulting inonly carbon dioxide and water as the ultimate products of the process.Wagner additionally teaches that the flame temperature associated withthe combustion of pure methane with pure oxygen can reach 6,000 degreesFahrenheit, (3,315.56 degrees Celsius). Wagner's invention is aspecialized boiler designed to maximize thermal efficiency with verysmall size and low weight per unit of energy derived. For refractorylined combustion chambers and standard energy recovery boiler systems,lower combustion gas temperatures are required. Typical refractorylimitations on continuous operating temperature are in the area of 2,500degrees Fahrenheit (1371.1 degrees Celsius). The present inventionutilizes pure oxygen for combustion, but additionally utilizes acombination of water injection and combustion gas recirculation tomoderate and control the combustion gas temperature achieved in thecombustion chambers.

The utilization of oxygen for combustion and water injection andrecirculated combustion gas to moderate combustion gas temperature avoidthe introduction of nitrogen into the combustion process. As taught byWagner, nitrogen in a combustion process leads to the formation ofpollution in the form of oxides of nitrogen (NOx). Since air is composedof roughly 80% nitrogen by volume, the present invention by designavoids the employment of air as the source of oxygen for combustion oras a means for moderating the combustion gas temperature in thecombustion chambers. Other reasons for avoiding use of air in thepresent invention are the fact that a high volume of combustion gaswould be produced per unit of fuel combusted and the resultingcombustion gas would contain a lower percentage of carbon dioxide makingcarbon dioxide recovery less efficient.

The following formulation and calculations detail the relationshipdiscussed above:combustion of methane with pure oxygenCH4+2O2=>CO2+2H2O

For each mole weight of methane two mole weights of oxygen are requiredfor stoichiometric combustion. One mole weight of methane equals 16atomic weight units while two mole weights of oxygen equals 64 atomicweight units. Each kilogram of pure methane then requires four kilogramsof pure oxygen for stoichiometric combustion resulting in 5 kilograms ofcombustion gas consisting of one mole weight of carbon dioxide and twomole weights of water. Carbon dioxide has a mole weight of 44 atomicweight units while water has a mole weight of 18 atomic weight units.The stoichiometric combustion of one kilogram of pure methane with pureoxygen then product (5×(44/80))=2.75 kilograms of carbon dioxide and(5×((2×18)/80)))=2.25 kilograms of water.

Typically, an excess amount of oxygen is supplied to a combustionprocess to provide greater opportunity for complete combustion of fuelsthan is afforded by a one to one stoichiometric ratio of oxygen to fuel.Depending on the fuel being combusted and the combustion processefficiency the typical amount of excess oxygen supplied is in the rangeof 5% to 10%. For this discussion and for ease of calculation consider a5% excess of oxygen for a practical combustion process. In such caseeach kilogram of pure methane would then require 4.2 kilograms of pureoxygen for combustion resulting in the production of 5.2 kilograms ofcombustion gas of which 0.2 kilograms is residual oxygen. By weightpercentage the combustion gas composition from this process would thenbe as follows:

Carbon Dioxide: (2.75/5.2) × 100 = 52.88462% Water: (2.25/5.2) × 100 =43.26923% Oxygen:  (0.2/5.2) × 100 = 3.84615%

Using the known heating value of methane, calculated approximatespecific heat capacities for the combustion gas constituents, anapproximate ambient temperature and an approximate resultant combustiongas temperature can be calculated. The following relationship applies:T _(GAS) =T _(AMB)+((Q _(REL) −Q _(LOSS))/C _(P))/M _(GAS))

Where T_(GAS)=Resultant Combustion Gas Temperature

-   -   T_(AMB)=Ambient Temperature    -   Q_(REL)=Thermal Energy Release Rate    -   Q_(LOSS)=Thermal Energy Loss Rate    -   C_(P)=Combustion Gas Specific Heat Capacity    -   M_(GAS)=Combustion Gas Mass Flow Rate

The published heat of combustion of methane is 21,520 BTU/LB (11,955.55Kilo Cal/Kilogram). This value takes into account the latent heat ofvaporization of the water produced in the combustion reaction and isapplicable for the above equation.

The heat capacity of a given gas varies with temperature and pressure.Working with a constant pressure the specific heat capacity withvariation due only to temperature can be derived, CP. For this analysisa constant pressure of one atmosphere may be assumed. Data are availablefor the gases of interest here at one atmosphere of pressure over therange of temperature to be encountered in a combustion process. CP forthese gases may be expressed as a polynomial function of the form,CP=a0+a1T+a2T2+a3T3= . . . anTn where T is the absolute temperature ofthe gas of interest. In the temperature range of 0 to 2,500° F. thefollowing fourth order polynomials with 99.0% confidence level have beenderived for the atmosphere constant pressure specific heat capacities ofthe noted gases:

Carbon C_(P(CO2)) = 0.155989405 + 0.000194244567 (T) − Dioxide:5.69601423 × 10⁻⁸ (T²) + 2.64619520 × 10⁻¹³ (T³) + 4.73867961 × 10⁻¹⁷(T⁴) KCal/Kg-° K Oxygen: C_(P(02)) = 0.194741234 + 9.17986378 × 10⁻⁵ (T)− 3.60408938 × 10⁻⁸ (T²) + 1.03017213 × 10⁻¹¹ (T³) − 3.13211436 × 10⁻¹⁵(T⁴) KCal/Kg-° K Water C_(P(H2O)) = 0.378246954 + 0.0002190970339 (T) −Vapor: 7.65417026 × 10⁻⁸ (T²) + 4.54506122 × 10⁻¹¹ (T³) − 1.22059215 ×10⁻¹⁴ (T⁴) KCal/Kg-° K Where T is temperature in degrees Kelvin.

Where T is temperature in degrees Kelvin.

FIG. 4 graphically depicts the relationship noted by these calculations.

The specific heat capacity of a mixture of gases can be approximated byscaling each individual gas constituent specific heat capacity to thatconstituent's mass percentage of the mixture and summing the valuesderived. A mixture composed of 52.88462% carbon dioxide, 43.26923% watervapor and 3.84615% oxygen will then have a resultant specific heatcapacity as follows:C _(P(MIXTURE))=0.5288462C _(P(CO2))+0.4326923C _(P(H2O)+)0.0384615C_(P(O2))These are the proportions calculated for the combustion gas producedfrom the complete combustion of methane with pure oxygen with a 5%surplus of oxygen being supplied. Knowing the amount of thermal energyreleased from the combustion reaction as sensible heat and the ambienttemperature at which the combustion gas constituents entered the processone can calculate both the specific heat capacity of the resulting gasmixture and the theoretical maximum combustion gas temperature.Considering that both the resulting gas temperature and the specificheat capacity of the gas mixture are interdependent variables, are-iterative process may be applied to calculate these parameters.

To avoid the high combustion gas temperatures noted by Wagner whileallowing the combustion process of the present invention to be used in apractical manner with standard combustion chamber construction andstandard energy recovery boiler equipment combinations of combustion gasrecirculation and water injection are utilized. Calculations have beencarried out to determine the appropriate quantities of combustion gasrecirculation and water injection required to achieve 2,500 degreesFahrenheit in the combustion chamber of the present invention. The datacharts and plots which follow detail the calculation results.

Table One below details the data derived from the calculations utilizedto produce FIG. 5.

TABLE ONE Relative Mass Flows For Methane-Oxygen Combustion WaterInjection & Recirculation To Maintain 2500 Deg. F. Extra H₂O Recirc.Injection Mass Total Mass Case One 6.426 0 11.626 Case Two 0 15.75 20.95Case Three 1 12.492 18.692 Case Four 2 9.75 16.96 Case Five 3 7.32 15.52Case Six 4 5.06 14.26 Case Seven 5 2.92 13.12 Case Eight 6 0.86 12.06

Note from the calculations and plotted data derived therefrom thatcontrol can be exercised over the quantity of combustion gas generatedper unit of fuel mass combusted while maintaining a moderate combustiongas temperature. Utilizing a combination of water injection andrecirculation of cooled combustion gas the total mass flow of combustiongas out of the combustion chambers can vary from 20.95 to 11.626 massunits per mass unit of methane fuel combusted with 1.05 timesstoichiometric oxygen while maintaining 2,500 degrees Fahrenheitcombustion gas temperature. These calculations assume a 10% loss ofthermal energy through the combustion chamber walls. The lowestcombustion gas mass flow is achieved with zero combustion gasrecirculation and water injection alone utilized to moderate combustiongas temperature. The latent heat of vaporization of water is utilized toadvantage in this case as a means of minimizing mass flow per unit offuel mass being combusted. Under circumstances where this type ofoperation is favored the present invention can be so operated. Otherwisesome combination of water injection and cooled combustion gasrecirculation will normally be utilized as the means to controlcombustion gas temperature in the combustion chambers.

As shown in FIG. 6, the highest level of carbon dioxide in thecombustion gas occurs with zero water injection and recirculation ofcombustion gas alone being utilized to moderate combustion gastemperature. In this case the level of carbon dioxide will reach 52.88%of the total combustion gas production rate. The lowest level of carbondioxide in the combustion gas occurs with zero recirculation and waterinjection alone moderating the combustion gas temperature. In this casethe level of carbon dioxide will drop to 23.65% of the combustion gasmass out of the combustion chamber.

Energy absorbed as latent heat of vaporization into water is notrecovered in the energy boiler of the present invention. This is adisadvantage of water injection to moderate combustion gas temperature.An advantage of water injection in addition to the reduced combustiongas volume is the fact that a portion of the water can readily becondensed by cooling the combustion gases with a groundwater indirectheat exchanger prior to the inlet of the of the carbon dioxide recoverysystem. By condensing a portion of the water vapor carried as aconstituent of the combustion gas the gas volume is reduced and acleansing effect is achieved for the combustion gas. As water dropletsform during condensation, particulate matter and acidic constituentsthat might be carried in the gas due to less than ideal fuel compositionare efficiently removed from the gas with the condensate. With a higherpercentage of water and increased condensation, higher efficiency gascleaning is achieved. When utilizing fuels that contain acid producingconstituents and constituents that result in particulate matterformation water injection enhances the combustion gas cleansing processbetween the energy recovery boiler and carbon dioxide recovery system ofthe present invention and is included in the preferred embodiment forthat reason. Additionally, the present invention includes a provisionfor an optional electron beam oxidation reactor to enhance the overallcombustion efficiency of the process. Water molecules produce OH radialsand atomic oxygen when bombarded by accelerated electrons. These highlyreactive molecules act as scavengers for dilute concentrations ofresidual and reformed organic compounds in the post combustion chambercombustion gas stream. Included in the organic compounds that might bepresent in the post combustion chamber combustion gas stream are dioxinsand furans. Destroying these compounds to avoid contamination of theprocess effluents from the present invention is high priorityconsideration.

As shown in FIGS. 7A and 7B, this embodiment of the process of thepresent invention begins by introducing a fuel stream 221, oxygen stream222, and a water stream 224 into primary combustion chamber 210 whereinthe hydrocarbons from the fuel are combusted to produce the combustionproduct of carbon dioxide, water, and other combustion gases. Primarycombustion chamber 210 has an ash separation section 260 for removing aportion of solid components including ash that result from thecombustion process. Combustion product 228 is then introduced into aseparation cyclone 262 to remove additional ash and solids. Separationcyclone 262 is of a variety commonly known to those skilled in the artof combustion process. Having had the ash and decontaminated soilremoved, combustion product stream 228 is then introduced into secondarycombustion chamber 220.

Preferably, secondary combustion chamber 220 is a vertical combustionchamber such as is known by those of ordinary skill in the art.Hydrocarbons from combustion product stream 228 are reacted with anadditional fuel stream 230, a second substantially pure oxygen stream232, and a second water stream 234 in secondary combustion chamber 220.Fuel streams 221 and 230 can be a variety of fuels or combinations offuels, including methane and other hydrocarbon-containing compounds,including hydrocarbon contaminated soils. Solids, ash and otherparticulate matter are removed from a bottom cone section 264 ofsecondary combustion chamber 220. Reaction product stream 238 exits fromthe top of secondary combustion chamber 220. Secondary combustionchamber 220 is included in the process of the present invention toproduce high combustion efficiency.

One feature of the process of this embodiment is the ability to recoverthe energy, in the form of heat, from reaction product stream 238.Preferably, an energy recovery boiler 214 is used to recover the heatenergy from reaction product stream 238. As those skilled in the artwould recognize, energy recovery boiler 214 is used to generate steam bytransferring the heat energy from reaction product 238 to a waterstream. A portion of stream 238 can be used in parallel with energyrecovery boiler 214 to heat other process streams through crossexchanges of energy. Alternatively, other forms of heat exchangers canbe used to recover the heat energy from reaction product stream 238 inplace of energy recover boiler 214. Removal of the heat energy fromstream 238 in recovery boiler 214 results in a cooler streamtemperature. Preferably, stream 238 is cooled to about 450 degreesFahrenheit.

Cooled reaction product stream 240 is then introduced into a bag house266 for removal of particulate matter from cooled reaction productstream 240. Bag house 266 is of a design commonly known and used bythose skilled in the art. Preferably, an activated carbon injector 268can be utilized along with bag house 266 to assist in removal ofparticulate matter.

Upon exiting bag house 266, cooled reaction product stream 240 isintroduced into combustion gas manifold 270. Fan 272 can be used toincrease the pressure of cooled reaction product stream 240 prior tointroduction into gas manifold 270.

In gas manifold 270, cooled reaction product stream 240 is split intothree streams. First stream 226 is recirculated to primary combustionchamber 210 to increase combustion efficiency. The amount ofrecirculating combustion gas introduced into primary combustion chamber210 can be controlled by control valve 274 or other means of regulatingstream volume. A second portion of gas is removed from combustion gasmanifold 270 and recirculated as gas stream 236 into secondarycombustion chamber 220. The volume of gas flow from stream 236 iscontrolled by a control valve 276 or other means of regulating flow.Recirculation of gas stream 236 is introduced to secondary combustionchamber 220 to increase the efficiency of secondary combustion chamber220.

The remaining portion of reaction product stream 240 exits combustiongas manifold 270 as stream 242. Stream 242 is essentially the productstream from the combustion portion of the process of the presentinvention. Stream 242 comprises carbon dioxide, water, along withvarious other impurities and unreacted components from the combustionprocess. Stream 242 is introduced into electron beam reactor 280 tobreak down residual dilute organic compounds contained within stream 242and to impart an electrical charge on any residual particulate matter instream 242. Electron beam reactor 280 is of a variety commonly known andavailable to those skilled in the art. Stream 242 exits electron beamreactor 280 directly into ozone oxidation chamber 282 where additionalcomponents are oxidized and aid removal of them from the gas stream.

Next, stream 242 is introduced into an electrostatic precipitator andcatalytic reactor 284. In precipitator 284, additional particulatematter is removed from stream 242 including the particulate matterelectrically charged by electron beam reactor 280.

Stream 242 is next introduced into acid scrubber system 286 to removeany remaining acidic constituents in the gas stream. Acid scrubbersystem 286 comprises an adiabatic quench 288 and pack bed absorber 290.Acid scrubber system 286 is of a design commonly known to those skilledin the art of purifying gas streams. An alkaline stream 292 is contactedthrough countercurrent flow to pack bed absorber 290 to react awayacidic components found in stream 242. Optionally, acid scrubber system286 may consist of a series of pack bed absorbers 290 to increasecontact efficiency. The brine stream 294, which results from a contactof the alkaline stream 292 with the acid gas components, can then befiltered in filtration system 296. Stream 294 is then concentrated indistillation brine concentrator 298 to produce, for example, amarketable 42% brine stream for use in downhole hydrocarbon production,particularly fracturing operations.

Upon exiting acid scrubber system 286, stream 242 is increased inpressure by fan 300 and introduced into indirect heat exchanger 302.Indirect heat exchanger 302 is of a variety commonly known to thoseskilled in the art of heat transfer. Preferably, ground water atapproximately 55° F. is used to condense the water vapor from stream242. The condensation of water vapor also removes most of any remainingforms of contamination in the gas stream. Additionally, a condensatestream 304 comprising the water and any residual contaminants isreturned to acid scrubber system 286 where it is combined with thebrine.

Carbon dioxide stream 246 is then introduced into recovery system 218.Initially, stream 246 is introduced to a refrigeration heat exchanger308. Stream 246 then enters carbon dioxide recovery system 310 whereliquid carbon dioxide is separated from any excess oxygen or nitrogenremaining in stream 246. Carbon dioxide recovery system 310 is of adesign commonly known to those of ordinary skill in the art. As can beseen, liquid carbon dioxide stream 248 can then be marketed as a productto those needing carbon dioxide streams.

Finally, gas discharge stream 250 comprising excess oxygen and anynitrogen originally introduced through fuel streams 220 and 230 can bedischarged to the atmosphere. When operated under conditions such asdescribed herein, gas discharge stream 250 is eliminated orsubstantially reduced in comparison to prior art combustion processes.

FIGS. 8A and 8B disclose an adaptation of the embodiment of the presentinvention disclosed in FIGS. 7A and 7B. Particularly, the process ofFIGS. 8A and 8B have been adapted to include plasma torches 320 and 322and emergency evacuation chamber 324. Plasma torches 320 and 322 are ofa variety commonly known to those skilled in the art. Emergencyevacuation chamber 324 is an additional safety feature to enhance thesafety associated with the process of the present invention.

By utilizing pure oxygen for combustion and employing water injectionand recirculated combustion gas to moderate combustion gas temperaturein the combustion chambers the present invention allows all products ofcombustion to be captured before emission into the environment. Thecaptured products of combustion include carbon dioxide, water, andexcess oxygen. When nitrogen is present in the fuels being combusted amix of oxygen with a fractional trace of nitrogen will be removedtogether. Provision is made in the present invention to maintain thehighest possible combustion efficiency to reduce the level of traceorganic compounds in the combustion gas. Provision is also made toremove with the highest efficiency possible any acidic and particulateconstituents produced by the combustion of less than ideal fuels in thecombustion chambers of the present invention allowing the recoverycarbon dioxide and residual oxygen.

Solvent Process

Referring back to FIG. 2, the solvent process 20 of the presentinvention utilizes the purified carbon dioxide stream 72 from thethermal process 10 as a super-solvent to remove hydrocarbon andchlorinated hydrocarbon contamination from moderately contaminated soils74. Use of the solvent process 20 allows treatment of moderatelycontaminated soil 74 without actual thermal treatment of the soil andwithout emissions. Contaminated soil 74 is introduced into a soilprocessor or separator where it is contacted with the carbon dioxidestream 72. Depending upon the level of hydrocarbon contamination, acarbon dioxide recycle stream 78 can be utilized to minimize the amountof carbon dioxide required for solvent process 20. The carbon dioxide isthen removed from the soil and decontaminated soil stream 76 can beremoved from the system and returned to the original site as clean soilor used as refill in other areas. The carbon dioxide containing thecontaminates can be sent to thermal process 10 for further treatment.Optionally, the carbon dioxide and contaminants can be separated in thesolvent process 20 and a contaminant stream 80 returned to the thermalprocess 10 while a recovered carbon dioxide stream 82 can be used inother processes.

Referring to FIG. 9, contaminated soil stream 74 is introduced into thesolvent process 20 through inlet 152. Soil stream 74 can be any type ofsoil or waste material contaminated with hydrocarbons. Generally, soilstream 74 has hydrocarbon contamination of less than 1% by volume.Typically, soil stream 74 has between about 20,000 and about 50,000mg/kg of total petroleum hydrocarbons (or “TPH”) as determined byEnvironmental Protection Agency, “EPA”, standard method 418.1.

Inlet 152 can be a funnel-shaped bin or other structure such as aninverted pyramid that directs soil towards a soil conveyor such as auger154. Auger 154 is preferably a screw auger such as is known to thoseskilled in the art. Auger 154 pushes hydrocarbon contaminated soilstream 74 forward and into soil processor vessel 160. Preferably, auger154 is a 24 inch auger capable of moving at least 60 cubic yards of soilper hour. Auger 154 allows introduction of the soil stream whilemaintaining a seal on vessel 160.

Soil processor vessel 160 is preferably designed to withstand 120 psigand a full vacuum. Soil processor vessel 160 is preferably constructedof steel, most preferably rolled A36 steel.

Soil processor vessel 160 preferably has three sections: a fixed end164; a rotating section 162; and a separation chamber 166. Preferably,soil processor vessel 160 is cylindrically shaped with a diameter of atleast three to four feet. Rotating section 162 of vessel 160 hasinternal baffles or paddles 163 configured in a helical or spiral-typeconfiguration to assist moving soil forward through vessel 160.Preferably, baffles 163 have apertures. Soil processor vessel 160 ispreferably angled relative to the horizontal. More preferably soilprocessor vessel is angled at between about 5 and about 25° relative tothe horizontal with the separation chamber 166 being higher than fixedend 164. Rotating section 162 operates similarly to a cement mixerrotating completely during the soil washing process.

Internal to soil processor vessel 160 is soil shaker 158. Soil shaker158 is of a variety commonly used on drillings rigs for screeningdrilling muds. Soil shaker 158 has a screen which is vibrated. As willbe recognized by those of skill in the art, the screen size on shaker158 can be varied in size depending upon soil makeup. Soil shaker 158preferably has a cylindrical screen having approximately six inches toone foot diameter smaller than a diameter of vessel 160. Preferably,soil shaker 158 rotates with rotating section 162 of vessel 160.

Auger 154 drops the soil upon soil shaker 158 inside soil processorvessel 160. Shaker 158 vibrates advancing the soil sifting a portion ofthe soil through the screen onto the inside of vessel 160. Shaker 158shakes the soil through the screen decreasing the particle size. Thisscreening process maximizes the amount of contact between thecontaminated soil and the carbon dioxide.

Carbon dioxide stream 72 is introduced through vessel inlet 156 onvessel 160. Preferably vessel inlet 156 is simple nozzle located the topof fixed end 164 of vessel 160. Carbon dioxide stream 72 is a liquidstream, preferably taken from the carbon dioxide recovered in thermalprocess 10. Preferably, carbon dioxide stream 72 is pumped into vessel160.

Rotating section 162 of vessel 160 rotates causing agitation andincreasing the contact between the carbon dioxide and soil. Further, therotation returns soil to the shaker 158 where it is again sifted andfurther exposed with carbon dioxide. Baffles 163 and the rotation ofsection 162 allow multiple passes of the soil through contact with thecarbon dioxide.

Preferably, vessel 160 is maintained between about 10% and 50% full ofliquid carbon dioxide. More preferably, vessel 160 is approximately 25%liquid full. A pressure controller 177 downstream of second end 166 ofvessel 160 maintains the pressure on the vessel to prevent the entirecarbon dioxide stream from flashing immediately upon entry to vessel160. Pressure controller 177 can be a restricting orifice, valve,automated valve, pressure regulator, or other pressure or gas flowcontrolling devices.

As the soil advances further up the shaker 158, out of the liquidcarbon, carbon dioxide evaporates off of each particle assisted by thesifting action.

Shaker 158 ultimately drops the contaminated soil through soil outlet168 where it is removed by a second soil conveyor such as auger 170where it can be returned to a clean soil bin 174 or other holding areas.Preferably auger 154 and 170 are of substantially equivalent design.

In experimental data using an embodiment of the present invention,contaminated soil was measured using EPA method 418.1 to determine thetotal petroleum hydrocarbons. Samples having from between about 46,000and about 180,000 milligrams per kilogram prior to introduction into theprocessor vessel 160 were reduce to non-detectable levels using anembodiment of the present invention as analyzed by EPA method 8020A(measuring micrograms per kilogram).

Carbon dioxide and extracted hydrocarbon contaminates exit vessel 160through line 176. The hydrocarbons, other contaminates, and entrainedsolids are removed from the carbon dioxide stream through a series ofvessels 178, 186, and 196. Separator vessel 178 has baffles 180 topromote separation. Preferably, line 176 enters separator vessel 178tangential to create a centrifuge effect. Entrained solids fall to thebottom of vessel 178 while condensed liquids exit separator vessel 178through outlet 184.

The remaining carbon dioxide and hydrocarbon stream is sent through line182 to vessel 186. Separator vessel 186 has a flash section 188 having atraditional “shotgun barrel” design which causes any entrained liquidcarbon dioxide to vaporize as well as assist separation of heavierhydrocarbon contaminants. Similarly to vessel 178, separator vessel 186has internal baffles 190 to assist in the separation process. Anyentrained solids will collect in the bottom of vessel 186 whilecondensed liquids are removed through line 194 and combined with liquidsin line 184. Optionally, a second separator vessel 196, of generally thesame construction as vessel 186 can be utilized if needed to removeadditional hydrocarbons from the carbon dioxide. Condensed liquids fromvessel 196 are removed through line 204 and combined with the liquidsfrom lines 184 and 194. This combined stream 206 can be directed tothermal incineration process such as thermal process 10. Vaporizedcarbon dioxide exiting the system through line 202 can be compressed andreturned to the carbon dioxide recovery system 310 as shown in FIG. 7A.

Experimental results indicate that approximately ten pounds of carbondioxide will dissolve and remove one pound of hydrocarbon contamination.Therefore a cubic yard of soil at typical contamination conditions willrequire approximately 10,000 standard cubic feet of carbon dioxide forthis process.

As shown in FIG. 10, the solvent process 20 of the present invention canbe a mobile installation. In this embodiment the process components aremounted on a mobile platform 400 such as a portable skid, a trailer, ora truck bed. Liquid carbon dioxide can be supplied to the process by atank truck 402. Carbon dioxide containing the extracted hydrocarbons canbe placed in a second tank truck 404 to be delivered back to thermalprocess 10. This process is particularly useful for sites requiring onlya few truckloads of soil to be decontaminated. This mobile embodimentcan be delivered directly to a site containing contaminated soil.Contaminated soil can be picked up, treated in a solvent process 20, andreturned without ever having to leave the contamination site. In thisembodiment, separator vessels 178, 186, and 196 are optional.

Other Process Systems

Referring back to FIG. 2, a vaporization process 50 can be used inconjunction with thermal process 10 and solvent process 20. In thisembodiment of vaporization process 20, lightly contaminated soil 92 issubjected to a vaporization process utilizing heat energy generated fromthermal process 10 to heat the soil and vaporize low boiling pointhydrocarbons such as gasoline. Steam 94 generated in thermal process 10can be used to heat oil or other heat transfer agents in heat exchanger98. Heat transfer agent stream 100 can then be used to heat soil stream92 in the vaporization process 50. Alternatively, steam 94 can be useddirectly to provide heat for the vaporization process 50. In eithercase, condensate stream 96 can be returned to thermal process 10.Vaporization process 50 can utilize a heat screw system in a partialvacuum environment or other similar techniques such as are known tothose skilled in the art for heating and mixing soils or materials ofsimilar consistencies. Vapor stream 104 generated in the vaporizationprocess 50 can be captured, condensed, and used as fuel for thermalprocess 10. Decontaminated soil stream 106 can be removed from thesystem and returned to the original site as clean soil or used as refillin other areas.

Any of the decontaminated soil streams 70, 76, or 106 that may containresidual metals can be further processed to remove the metalcontamination. These streams can be washed with a dilute acid solution118 in a soil acid rinsing process 108 to leach out the residual metalsuntil an acceptable level of contamination is reached. The acid washedsoil stream 110 exiting the rinsing process 108 can be mixed with acalcium hydroxide lime stream 114 in a mechanical blender 112 toneutralize residual acid. Decontaminated soil stream 116 can be removedfrom the system and returned to the original site as clean soil or usedas refill in other areas.

Rinsate stream 120 can also be neutralized using a lime stream 124 in aneutralization process 122. Hydroxides of the metals rinsed from thesoils and dissolved into the acid rinsate stream 120 are formed when therinsate 120 is treated by the addition of calcium hydroxide lime stream124. These metal hydroxides can be removed from the neutralized rinsatestream 126 utilizing both a Lamella clarifier 128 and a filter press130. The spent filter cake stream 132 containing the metal hydroxidescan then be mixed with the fly ash stream 134 from the thermal process10 and/or a Portland cement stream 136 in a mixer and block moldingprocess 138 for stabilization and disposal.

In Situ Decontamination

One alternative process in which either recovered carbon dioxide stream84 from thermal process 10 or recovered carbon dioxide stream 82 fromsolvent process 20 can be used involves cleaning soil in place. Thisalternative process utilizes carbonic fluids injection and recovery welltechniques to recover hydrocarbon contamination that has leached fromthe soil into the subsurface water supply. Carbon dioxide stream 88 isintroduced into a carbon dioxide injection monitoring well 86 where thecarbon dioxide is released into a subsurface formation. The carbondioxide picks up hydrocarbons from the formations and accumulates insubsurface water. Multiple adjacent wells can be used to recover a waterand carbon dioxide stream 90 containing the hydrocarbon contamination.Stream 90 is pumped to the surface and treated in the thermal process 10where the hydrocarbons are converted into carbon dioxide and water withno emissions while all contamination is neutralized and turned intocommercial byproducts. Stream 90 can be utilized in thermal process 10as quench water stream 68 to moderate combustion chamber temperature.

As will now be recognized, the present invention includes a combinationof processes to remove hydrocarbon and other contaminants from soil.Preferably, heavily contaminated soils will be treated in thermalprocess 10. Soils with medium contamination will be treated in solventprocess 20 utilizing carbon dioxide generated in thermal process 10 asthe solvent. Lightly contaminated soils can be treated in vaporizationprocess 50 utilizing heat energy from thermal process 10 to vaporizecontaminants. Additionally, excess carbon dioxide from the thermalprocess 10 can be injected into monitoring wells to clean hydrocarbonsfrom contaminated subsurface formations and water.

The foregoing disclosure and description of the invention areillustrative and explanatory thereof, and various changes in the detailsof the illustrated apparatus and construction and method of operationmay be made without departing from the spirit of the invention.

1. A process for removing hydrocarbons from hydrocarbon contaminatedmaterials, comprising the steps of: providing a processing vessel;introducing hydrocarbon contaminated materials into the processingvessel; screening the hydrocarbon contaminated materials into finerparticles within the processing vessel; introducing liquid carbondioxide into the processing vessel; contacting the hydrocarboncontaminated materials with the liquid carbon dioxide; extracting thehydrocarbons from the hydrocarbon contaminated materials using theliquid carbon dioxide as an extractant; separating the carbon dioxideand the extracted hydrocarbons from the hydrocarbon contaminatedmaterials to produce treated materials; and removing the treatedmaterials from the processing vessel.
 2. The process of claim 1, furthercomprising the step of separating the extracted hydrocarbons from thecarbon dioxide used as an extractant.
 3. The process of claim 1, furthercomprising the step of rinsing the treated materials removed from theprocessing vessel with an acid solution to remove residual metals. 4.The process of claim 1, wherein the processing vessel comprises a fixedsection and a section that rotates.
 5. The process of claim 1, whereinthe hydrocarbon contaminated materials comprise hydrocarbon contaminatedsoil.
 6. The process of claim 1, wherein the hydrocarbon contaminatedmaterials comprise hydrocarbon contaminated waste.
 7. The process ofclaim 1, wherein the introducing hydrocarbon contaminated materials stepcomprises conveying the hydrocarbon contaminated materials into theprocessing vessel.
 8. The process of claim 1, wherein the hydrocarboncontaminated materials comprise less than about 1% by volumehydrocarbons.
 9. The process of claim 1, wherein about ten pounds of theliquid carbon dioxide are introduced for every pound of hydrocarbonintroduced in the hydrocarbon contaminated materials.
 10. The process ofclaim 1, wherein the introducing the liquid carbon dioxide stepcomprises pumping the liquid carbon dioxide into the processing vessel.11. The process of claim 4, further comprising the step of rotating therotating section of the processing vessel to enhance contact of theliquid carbon dioxide with the hydrocarbon contaminated materials. 12.The process of claim 1, wherein the providing step comprises providing amobile processing vessel.
 13. The process of claim 1, wherein thescreening step comprises screening the hydrocarbon contaminatedmaterials using a soil shaker.
 14. The process of claim 1, wherein theproviding step comprises providing a processing vessel at an angle ofabout 5 degrees to about 25 degrees from the horizontal.
 15. A processfor removing hydrocarbons from hydrocarbon contaminated soil, comprisingthe steps of: providing a soil processing vessel having a first fixedend, a section that rotates, and a second end; introducing hydrocarboncontaminated soil into the soil processing vessel; screening thehydrocarbon contaminated soil inside the soil processing vessel;introducing liquid carbon dioxide into the soil processing vessel;contacting the hydrocarbon contaminated soil with the liquid carbondioxide; and extracting hydrocarbons from the hydrocarbon contaminatedsoil using the liquid carbon dioxide as an extractant; separating thecarbon dioxide and the extracted hydrocarbons from the hydrocarboncontaminated soil to produce treated soil; and removing the treated soilfrom the soil processing vessel.
 16. The process of claim 15, furthercomprising the step of rotating the rotating section of the soilprocessing vessel to enhance contact of the liquid carbon dioxide withthe hydrocarbon contaminated soil.
 17. The process of claim 15, whereinthe providing step comprises providing a mobile soil processing vessel.18. The process of claim 15, wherein the providing step comprisesproviding a soil processing vessel at an angle of about 5 degrees toabout 25 degrees from the horizontal.
 19. The process of claim 15,further comprising the step of rinsing the treated soil removed from thesoil processing vessel with an acid solution to remove residual metals.20. The process of claim 15, further comprising the step of separatingthe extracted hydrocarbons from the carbon dioxide used as anextractant.